This invention relates to cyclohexenylmethyloxabicyclooctanes defined according to the generic structures: ##STR3## as well as intermediates for producing same defined according to the generic structures: ##STR4## as well as organoleptic uses of said cyclohexenylmethyloxabicyclooctanes and intermediates therefor in augmenting or enhancing the aroma of perfume compositions, colognes and perfumed articles, wherein R.sub.1, R.sub.2, R.sub.3 ' and R.sub.3 " each represents hydrogen or methyl with the provisos:
(i) one or both of R.sub.1 and R.sub.2 represents methyl; PA0 (ii) when R.sub.1 and R.sub.2 are both methyl, then R.sub.3 ' and R.sub.3 " are both hydrogen; PA0 (iii) one of R.sub.3 ' and R.sub.3 " is methyl and the other is hydrogen or R.sub.3 ' and R.sub.3 " both represent hydrogen; and PA0 (iv) when R.sub.3 ' or R.sub.3 " represents methyl then R.sub.1 is methyl and R.sub.2 is hydrogen PA0 "Fresh, diffusive, camphoraceous-cool odor of poor tenacity. Sweet and fresh, cool-camphoraceous taste and cool mouthfeel unless very highly concentrated. PA0 Widely used in perfume compositions for its refreshing effect in herbaceous type fragrances, Lavender, New Mown Hay, Fougere, etc. and in medicinal type odors for soap and household products. Also, in masking odors for industrial purposes, unless Eucalyptus oil must be used for its lower cost. PA0 This oxide has found increased usage during the 1965/66 period of abnormally high prices for Lavandin and Spike Lavender oils. PA0 The odor of Eucalyptus is, in some countries, rated synonomous with masking odors for lavatories, etc., a fact which has an unquestionable psychological effect, causing people to reject the odor of Eucalyptus for oral-hygienic purposes, etc. Similar viewpoints has been observed about the use of Methylsalicylate in dentifrice in many European countries. Peculiarly enough, Methylsalicylate is still a popular candy-, soft-drink- and toothpaste flavor in the U.S.A, where the ester at the same time is used as a masking agent in toilet-bowl cleaners! PA0 The `olfactory association` is quite human and common, but it may at times completely destroy the chances of a chemical from its use in flavors or other field. PA0 Eucalyptol is extensively used in flavor compositions, particularly in all types of preparations for oral hygiene, dentifrice, breath-sprays, mouthwashes, cough lozenges, pastilles, skin-rubbing lotions, inhalator fluids, etc. PA0 It seems, however, that its use in skin rubbing lotions has hampered its popularity as a candy flavor in the U.S.A. PA0 Normal use concentrations are about 1 to 15 ppm in the finished (flavored) product, but concentrations as high as 200 ppm are found in chewing gum."
and R.sub.4 ' is hydrogen or C.sub.1 -C.sub.5 alkyl.
There had been considerable work performed relating to substances which can be used to impart, modify, augment or enhance fragrances with regard to perfume compositions, perfumed articles and colognes. Earthy, green, animalic and musky aromas with earthy and green topnotes are particularly desirable in augmenting or enhancing the aroma of perfume compositions, colognes and perfumed articles (e.g., solid or liquid anionic, cationic, nonionic or aqitterionic detergents, fabric softener compositions, fabric softener articles, hair preparations, cosmetic powders and perfumed polymers.
Oxabicyclooctanes having various substituents are known for use in perfumery. Thus, Arctander in "Perfume and Flavor Chemicals (Aroma Chemicals)", Vol. I, 1969 at monograph No. 616 describes 1,8-cineole having the structure: ##STR5## as being useful in perfumery and in flavor compositions. Thus, Arctander states, regarding 1,8-cineole:
Sprecker, et al. in U.S. Pat. No. 4,269,862 at column 3, lines 30-33 discloses the genus of compounds defined according to the structure: ##STR6## wherein R.sub.1 is hydrogen or methyl and wherein R.sub.2 is C.sub.1 -C.sub.5 alkyl or alkenyl as having perfume utility. Furthermore, Sprecker, et al. discloses at column 4, lines 35-40 the compound having the structure: ##STR7## as having a minty, camphoraceous, woody and piney aroma useful in augmenting or enhancing the aroma of perfume compositions, colognes and perfumed articles.
Sprecker, et al. further discloses the reaction: ##STR8## in preparing such oxabicyclooctane derivatives. Sprecker, et al., U.S. Pat. No. 4,267,067 discloses the reaction: ##STR9## in preparing oxabicyclooctane derivatives useful in augmenting or enhancing the aroma of perfume compositions, colognes and perfumed articles.
Nothing in the prior art, however, discloses the cyclohexenylmethyloxabicyclooctanes of our invention or intermediates therefor or uses of said cyclohexenylmethyloxabicyclooctanes or intermediates therefor in augmenting or enhancing the aroma of perfume compositions, colognes and perfumed articles.